Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized <i>N</i>,<i>S</i>‐Heterocycles
Guang‐Yu Zhu, Ji‐Jia Zhou, Li‐Gao Liu, Xiao Li, Xin‐Qi Zhu, Xin Lü, Jin‐Mei Zhou, Long‐Wu Ye
Abstract
Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement of sulfoxide-ynamides, enabling divergent and atom-economic synthesis of a series of valuable medium-sized N,S-heterocycles in moderate to good yields with broad substrate scope. Importantly, excellent enantioselectivities have been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations are employed to elucidate the origins of the catalyst-dependent stereospecific [3,3]-rearrangement.